The present invention relates to quaternary ammonium compounds and formulations thereof useful as, for instance, cleaning compositions, antistatic compounds, fabric softeners, hair conditioners, skin conditioners, paper deinking and ink floatation agents, asphalt emulsion agents, corrosion inhibitor agents, ore floatation agents, pesticide emulsion agents, car drying aid sprays, drilling fluid additives, and the like.
Heretofore quaternary ammonium compounds and a very few dialkyl ammonium compounds (xe2x80x9cconventional quatsxe2x80x9d) have found widespread use in many applications. For example, a variety of conventional quats have been proposed for many uses, for example, in fabric softeners for home use or for industrial and institutional use. In general, such compounds exhibit properties which present some difficulty in the manufacture, formulation use, aesthetic properties, biodegradability, and environmental compatibility of these compositions. For example, many of the conventional compositions used for these functions, even if completely biodegradable with time, do not biodegrade as rapidly as could be desired and are thus not considered readily biodegradable. In addition, several of the commercial readily biodegradable softeners, conditioners, and debonders do not function as effectively as the conventional products that are less biodegradable. Thus, to maintain effective levels of performance, increased amounts of such less effective, more readily biodegradable products (such as softeners) must be employed and, as will be readily apparent, this factor decreases the cost-effectiveness of the product.
The relatively poor solubility of conventional quats also contributes to certain difficulties that will vary, depending on the application. For example, when such conventional quats are used in fabric softeners, their poor solubility inhibits the dispersibility of the fabric softener actives into water and the dispersibility of the formulated fabric softener product into the washing machine.
Thus, there remains a need for identification of new amine and ammonium derivatives, and particular quaternary derivatives, which are useful as fabric softeners and which are also biodegradable, highly effective in softening, debonding, conditioning, and the like, and yet avoid these problems upon manufacture, formulation and use. It is also desirable for the active agents used in hair and skin conditioners, textile softeners, and the like, to be readily biodegradable and to exhibit a satisfactorily high activity. Conventional products have to date not been able to exhibit both properties to a high degree, thus necessitating acceptance of reduced biodegradability or reduced activity. There is thus still a need for compounds exhibiting levels of activity as conditioners, and so on, as the case may be, which are comparable or superior to conventionally employed actives, such as conventional quats, while also exhibiting ready biodegradability.
As can be appreciated, the chemistry of fabric softeners, hair conditioners, skin conditioners, textile softeners, car wax sprays, and the like is challenging. Each of these applications presents its own complications, because the interactions between the various components of the compositions must be considered in addition to the individual chemistry of each component.
For example, considering the fabric softening application, the detergent compounds with the widest range of cleaning properties are generally anionic (negatively charged) surfactants. Such anionic surfactants, for example, may include the alkylbenzene sulfonates, xcex1-olefin sulfonates, and xylene sulfonates available from Witco Corporation under the WITCONATE(copyright) trademark. In contrast, as exemplified by the amine and ammonium compounds discussed above, fabric softening compounds are generally cationic (positively charged). Thus, when the anionic detergent ingredients and cationic softening ingredients are present in the same aqueous solution, they have a natural tendency to complex together or even precipitate out of solution. This complexation or precipitation reaction interferes with the performance of both the detergent compounds and the softening compounds and is therefore undesirable. It can be readily appreciated that this undesirable complexation or precipitation reaction may occur if both detergent and softener compounds are added together in a wash cycle; however, as North American washing machines typically rinse the clothes only once before fabric softener is added to the washload, even if the fabric softener is added during a rinse cycle (as is typically done), residual anionic detergent compounds (including builders) present in the fabric complexes with the cationic softener compounds.
The present invention achieves these objectives and also exhibits the properties and advantages described herein. The present invention relates to quaternary ammonium compounds and formulations thereof useful as, for instance, cleaning compositions, antistatic compounds, fabric softeners, hair conditioners, skin conditioners, paper deinking and ink floatation agents, asphalt emulsion agents, corrosion inhibitor agents, ore floatation agents, pesticide emulsion agents, car drying aid sprays, drilling fluid additives, and the like.
In washing of textiles the well-known so-called rinse softeners are often used in the last washing stage. In this way, coarsening of the fabric is lessened which otherwise could be realized upon drying. The feel of textiles treated in this way such as hand and bath towels as well as clothes and bed linens is pleasantly improved.
Cationic compounds are customarily used as rinse softeners, for example, quaternary ammonium compounds which can contain long-chain alkyl groups as well as ester groups or amide groups, such as are described in U.S. Pat. Nos. 3,349,043; 3,644,203; 3,946,115; 3,997,453; 4,073,735; and 4,119,545. These quaternary ammonium compounds are added to the rinse water by themselves or in mixtures with other cationic or neutral compounds in the form of aqueous dispersions.
In addition, ammonium compounds which contain ester linkages are frequently used, such as are described in EP-A-023910, U.S. Pat. No. 3,915,867; U.S. Pat. No. 4,137,180; and U.S. Pat. No. 4,830,771. Particularly widely used are ester compounds based on triethanolamine such as N-methyl, N,N-bis(xcex2-C14-18-acyloxyethyl), N-xcex2-hydroxyethyl ammonium methylsulfate, which are available from Kao Corporation under tradename TETRANYL(copyright) AT 75, from Stepan Corporation under the tradename STEPANTEX(copyright) ZRH 90, and from Witco Surfactants GmbH under the tradename REWOQUAT(copyright) WE 18.
While these cationic compounds exhibit effective softening when used in the last rinse stage, they exhibit some disadvantages during use. For example, one disadvantage is that a relatively large amount of softening agents is required to simultaneously obtain good rewettability and soft feel of textiles, although the softness is still unsatisfactory. Rewetting power or rewettability is generally taken to mean the absorption of moisture by the fiber. Inadequate rewetting power is, however, disadvantageous wherever relatively large amounts of moisture are to be absorbed from the surface of the skin, for example, in the case of hand or bath towels and in the case of underwear or bed linen. However, batch or continuous processes are known that can be used to prepare stable fabric softener dispersions using these products.
An object of the present invention was to overcome the abovementioned disadvantages of traditional fabric softener formulations and to provide laundry fabric softeners which, in addition to good biodegradability, have a significantly improved level of simultaneously good soft handle and rewetting power. This object was achieved using quaternary fatty acid amino alcohol esters of methylethanolisopropanolamine (MEIPA) with fatty acids in the ratio of from 1:1.5 to 1:2 with use of monofunctional alcohols or bifunctional alcohols.
The instant invention provides quaternary ammonium compounds of the general formula (I) 
and of the general formula (II) 
wherein R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5;
R1, R2, and R3 are each independently of one another fatty acid radicals having 6-22 carbon atoms; and
Axe2x88x92 is an inorganic or organic anion. In general, Axe2x88x92, whether shown or understood, may be selected, without limitation, from the group consisting of fluoride, chloride, bromide, iodide, chlorite, chlorate, hydroxide, hypophosphite, phosphite, phosphate, carbonate, formate, acetate, lactate, and other carboxylates, oxalate, methyl sulfate, ethyl sulfate, benzoate, and salicylate, and the like. Preferred examples of the anions are chloride, bromide, methyl sulfate, ethyl sulfate, and salicylate. The invention also provides compositions comprising quaternary ammonium compounds of the general formula (I) and/or (II); in preferred embodiments of such compositions the amount of quaternary ammonium compounds of the general formula (I) and/or (II) generally ranges from about 2 wt. % to about 80 wt. %, preferably 5 wt. % to 30 wt. %, and more preferably 6 wt. % to 25 wt. %, of the total composition. The invention additionally provides compositions comprising quaternary ammonium compounds of the general formula (I) and/or (II) in combination with conventional quaternary ammonium compounds that comprise from about 10% to about 90% by weight of the total amount of quaternary ammonium compounds, which is the quaternary ammonium compounds of the general formula (I) and/or (II) and the conventional quaternary ammonium compounds, in the composition. Other preferred embodiment of the instant invention comprises quaternary ammonium compounds of the general formula (I) and/or (II) in combination with water.
The invention further provides quaternary ammonium compounds of the general formulas (I) and (II) which can be prepared by esterification of MEIPA with fatty acids in the molar ratio of from 1:1.5 to 1:2 and subsequent quaternization carried omit under conditions well known in this field for quaternization of amines, by reaction of the esterified amine with a suitable quaternizing agent.
The invention further provides aqueous fabric softeners comprising at least one of the compounds of the general formula (I) and/or (II). In such application, the fabric softener composition is contemplated to be applied in any of the many conventional ways fabric softeners are applied to fabrics. For example, the fabric softener compositions of the instant invention may be applied or used at any time in the wash cycle of a washing machine, for example, in a prewash cycle, wash cycle, or postwash (rinse) cycle by adding such composition to the wash or rinse water or spraying directly on the clothes. In addition, the fabric softener compositions of the instant invention may be applied or used at any time previous or subsequent to the fabric being placed in a washing machine, for example, in a clothes dryer by use of a fabric softener dryer sheet impregnated with one of the compounds of the general formula (I) and/or (II), or by spraying a formulation comprising one of the compounds of the general formula (I) and/or (II) on the fabric at any time before or after washing.
The invention also provides personal care compositions comprising quaternary ammonium compounds of the general formula (I) and/or (II), which may optionally include from about 1% to about 20% by weight of a secondary surfactant selected from the group consisting of: nonionic surfactants, amphoteric surfactants, zwitterionic surfactants, and ionic surfactants. In preferred embodiments, the secondary surfactant is selected from the group consisting of: ammonium lauryl sulfate, sodium lauryl sulfate, any xcex1-olefin sulfonate, ammonium laureth sulfate (2 or 3 moles), sodium laureth sulfate (2 or 3 moles), sodium myristyl sulfate, sodium myristeth sulfate (14 moles), ammonium xylene sulfonate, sodium xylene sulfonate, TEA dodecylbenzene sulfonate, TEA lauryl sulfate, ammonium pareth sulfate, sodium pareth sulfate, sodium oleth sulfate, derivatives thereof, and mixtures thereof. In other preferred embodiments, the secondary surfactant is selected from the group consisting of: betaines, sulfosuccinates, mono- and diglycerides, glycinates, sugars and derivatives thereof, hydroxysultaines, mono- and diacetates, ethoxylated derivatives thereof, and mixtures thereof. In yet other preferred embodiments, the secondary surfactant is selected from the group consisting of: alkanolamides; amine oxides; nonylphenol ethoxylates; C5-C20 linear or branched alcoxylates using EO, PO, BO, or mixtures thereof; amine ethoxylates; fatty amide ethoxylates; fatty acid ethoxylates; carboxylated nonionics; xcex1-polyglucosides; and mixtures thereof. In still other preferred embodiments, the formulation further comprises water and/or about 0.1% to 10% by weight of thickeners, perfumes, preservatives, dyes, plant extracts and other additives and auxiliaries.
The invention further provides for the use of compounds of the general formulas (I) and/or (II) in amounts of 1-5% by weight for the preparation of hair or skin conditioner compositions with use of auxiliaries and additives customary in this field. Hair or skin conditioner compositions are taken to mean applications such as hair treatments, hair rinses, hair balsam, hair mousses, spray lotions for improving combability, conditioning shampoos, shower gels, and liquid soaps having a smoothing effect on the skin.
The invention further provides for the use of 5-20% by weight of the compounds of the general formula (I) and/or (II) for the preparation of detergents and rinses and drying auxiliaries for motor vehicles with use of the additives and auxiliaries customary in this field, such as solvents, viscosity regulators, fatty acid esters, and additional surfactants.
The quaternary ammonium compounds of the general formulas (I) and/or (II) can, in combination with other surfactants and/or silicone compounds, be used as hydrophilic handle modifiers for yarns, fabrics and other textiles made from synthetic and mixed fibers and, preferably, from natural fibers, in which case they impart excellent antistatic properties, good handle, and hydrophilicity to the textiles without causing yellowing. The handle modifiers are used as 1-10% strength dispersions, coverage being 1-15%. The invention thus further provides for the use of the compounds of the general formulas (I) and/or (II) for the preparation of hydrophilic handle modifiers for yarns, fabrics and other textiles, comprising 15% to 25% by weight of alkyl fatty acid polyglycol ester having 6 to 25 moles of EO, 45% to 65% by weight of quaternary ammonium compounds of the general formula (I) and/or (II), 10-20% by weight of partial glyceride esters having 5 to 80 moles of EO, and 5% to 10% by weight of alkyl ether citrates (monoesters, diesters, and triesters having a degree of ethoxylation of 5 to 15), with the proviso that the components total 100% by weight. In preferred embodiment, the hydrophilic handle modifier compositions further comprise 0.001% to 10% by weight of silicone compounds; most preferably from about 0.01% to about 5% by weight of silicone compounds. In another preferred embodiment of the invention, the silicone compounds comprise silicone compounds of the polydimethylsiloxane and cationically-modified polydimethylsiloxane type.
The quaternary ammonium compounds of the general formula (I) and/or (II) can be used as such or in combination with other surfactants and/or silicone compounds as preparations for the permanent hydrophilization of polyolefin or polyester fibers and filaments and the nonwovens prepared therefrom. The permanent hydrophilization compositions are used as 1% to 10% strength dispersions, coverage being 1% to 15%. The surface-active constituents which are also used are preferably based on vegetable raw materials. The invention thus further provides for the use of the compounds of the general formula (I) and/or (II) for the preparation of permanent hydrophilization compositions comprising: 15% to 30% by weight of alkyl fatty acid polyglycol esters having 6 to 25 moles of EO; 45% to 65% by weight of quaternary ammonium compounds of the general formula (I) and/or (II); and 5% to 10% by weight of alkyl ether citrates (monoesters, diesters, and triesters having a degree of ethoxylation of 5 to 15), with the proviso that the components total 100% by weight. In preferred embodiment, the permanent hydrophilization compositions further comprise 0.001% to 10% by weight of silicone compounds, most preferably from about 0.01% to about 5% by weight of silicone compounds. In another preferred embodiment, the silicone compounds comprise silicone compounds of the polydimethylsiloxane and cationically-modified polydimethylsiloxane type.
The invention also provides a detergent, rinse, or drying auxiliary formulation for cars, comprising: (a) from about 5% to about 20% by weight of at least one quaternary ammonium compound selected from the group consisting of compounds of the general formula (1) and the general formula (II); and (b) from about 1% to about 20% by weight of a secondary surfactant selected from the group consisting of: nonionic surfactants, amphoteric surfactants, zwitterionic surfactants, and ionic surfactants, and blends thereof. In preferred embodiments, the secondary surfactant is selected from the group consisting of: alkylbenzene sulfonates, xcex1-olefin sulfonates, and xylene sulfonates.
The present invention also provides a composition comprising: (a) at least one quaternary ammonium compound selected from the group consisting of compounds of the general formula (I) and the general formula (II); (b) a solvatrope or coupling agent or blends thereof; and (c) an oil or hydrophobic organic component and blends thereof. In a preferred embodiment of the invention, the composition further comprises water. In yet another preferred embodiment of the invention, the amount of the compound of formula (I) and/or (II) is about 0.1 wt. % to about 65 wt. % of the formulation; the amount of solvatrope or coupling agent is about 0.1 wt. % to about 65 wt. % of the formulation, the amount of oil or hydrophobic organic component is about 0.1 wt. % to 65 wt. % of the formulation, and the amount of water is about 20 to 99.7 wt. % of the formulation, preferably about 35 wt. % to about 99.7 wt. %. In still other preferred embodiments of the invention, the composition comprises a mixture of two or more different solvents or coupling agents or the solvatrope or coupling agent is selected from the group consisting of: hydroxypivalyl hydroxypivalate and its alkoxylated derivatives, TMPD, TMPD alkoxylates, ethanol, isopropanol, butanol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, HPHP glycol, isopentyldiol, 1,2-hexanediol, ethylene glycol butyl ether, hexylene glycol, isoprene glycol, sorbitan ethoxylates, 2-butoxyethanol, C6-C12 diols/triols and ester diols/triols and their alkoxylated derivatives, glycol ethers, and mixtures thereof. In another preferred embodiment of the invention, the oil or hydrophobic organic component is selected from the group consisting of: fatty acids; fatty amides; fatty alcohols; fatty oils; fatty esters made from a C8-C22 fatty acid and a C1-C8 alcohol; dialkyl esters; mineral oil; mineral seal oils; silicone oils; petrolatums; monoglycerides; diglycerides; triglycerides; aliphatic, paraffinic, and naphthalinic hydrocarbons; oils and spirits; and mixtures thereof. In yet another preferred embodiment of the invention, the composition comprises a personal care emollient, which may be selected from the group consisting of: acetylated lanolin, aminopropyl dimethicone, ammonium hydrolyzed collagen, ammonium lauroyl sarcosinate, amodimethicone, amodimethicone/dimethicone copolyol, amodimethicone hydroxystearate, capryloyl hydrolyzed collagen, cetyl alcohol, cetyl esters, cetyl laurate, cocamidopropyl dimethylamine dihydroxymethylpropionate, cocoyl hydrolyzed soy protein, collagen, disodium cocoamphodiacetate, disodium cocoamphodipropionate, dioctyl dimerate, ditridecyl adipate, glycerine, glyceryl oleate, glyceryl stearate, hydrogenated soybean oil, hydrogenated tallow glycerides, isocetyl stearate, jojoba (Buxus chinensis) oil, keratin, lanolin, milk protein, mineral oil, oat (Avena sativa) protein, octyl cocoate, oleyl myristate, oleyl stearate, palm alcohol, palm glycerides, panthenol, PEG-10, PEG-32, PEG-100, PEG-200, petrolatum, PPG-6-sorbeth-245, stearyl citrate, tridecyl stearate, urea, vegetable oil, wheat amino acids, and mixtures thereof. In another preferred embodiment of the invention, the composition further comprises a personal care emulsifier, which may be selected from the group consisting of: beheneth-5, beheneth-10, beheneth-20, butylglucoside caprate, ceteareth-2, ceteareth-10, ceteareth-18, ceteth-10, ceteth-16, corn oil PEG-8 esters, C9-14 pareth-3, C11-15 pareth-5, C11-15 pareth-12, C12-13 pareth-2, C12-13 pareth-10, C12-13 pareth-15, deceth 4, deceth-5, deceth-6, di-C12-13 pareth-6 phosphate, di-C12-15 pareth-8 phosphate, glyceryl cocoate, glyceryl laurate, glyceryl oleate, isoceteth-10, isodeceth-6, isosteareth-10, laureth4, laureth-5, laureth-10, octyldodeceth-10, octyldodeceth-20, oleoyl ethyl glucoside, oleth-2, oleth-4, PEG-8 caprate, PEG-8 castor oil, PEG-7 cocamide, PEG-11 cocamide, PEG-15 cocoate, PEG-20 dilaurate, PEG-32 dilaurate, PEG-8 dioleate, PEG-2 distearate, PEG-8 distearate, PEG-8 glyceryl laurate, PEG-15 glyceryl laurate, PEG-4 isostearate, PEG4 laurate, PEG-5 octanoate, PEG-9 oleamide, PEG-5 oleate, PEG-20 palmitate, PEG-6 stearate, PEG-16 tallate, polysorbate 20, polysorbate 80, steareth-10, trideceth-5, undeceth-9, and mixtures thereof. In yet other preferred embodiments, the composition is emulsified into a microemulsion or is clear. In a preferred embodiment of the invention, the amount of the compound of formula (I) and/or (II) is about 5 wt. % to about 50 wt. % of the formulation, the amount of solvatrope or coupling agent is about 2 wt. % to about 15 wt. % of the formulation, and the amount of oil or hydrophobic organic component is about 5 wt. % to 50 wt. % of the formulation.
The quaternary compounds of the general formula (i) and (II) which are used according to the invention are prepared by the processes generally known in this field by esterification of methylethanolisopropanolamine 
with fatty acid and subsequent quaternization.
Fatty acids used for the esterification or transesterification are the monobasic fatty acids based on natural vegetable and animal oils having 6-22 carbon atoms, in particular having 14-18 carbon atoms, which are customary and known in this field, such as, in particular, rapeseed oil fatty acids, palm, tallow, castor fatty acids in the form of their glycerides, methyl or ethyl esters or as free acids.
The extent of unsaturation in these fatty acids or fatty acid esters is, as far as desired, adjusted to a desired iodine value by known catalytic hydrogenation processes, or achieved by mixing fatty components which are completely hydrogenated with fatty components which are not completely hydrogenated.
The iodine value (I.V.), a measure of the mean degree of saturation of a fatty acid, is the amount of iodine which is absorbed by 100 grams of the compound to saturate the double bonds.
Preferred according to the present invention are tallow fatty acids and palm fatty acids with iodine values between 15 and 50. These are commercially available products and can be obtained from various firms under the respective trade names for these products.
According to the invention, preference is given to tallow fatty acids and palm fatty acids having iodine values between 1-50 and rapeseed oil fatty acids having iodine values between 80-120. They are commercially available products and are supplied by various companies under their respective tradenames.
The esterification or transesterification is carried out using known processes. The methylethanolisopropanolamine is reacted with the amount of fatty acid or fatty acid ester corresponding to the desired degree of esterification, optionally in the presence of a catalyst, for example, methanesulfonic acid, under nitrogen at 160-240xc2x0 C., and the water of reaction which forms and the alcohol is continuously distilled off, it being possible to bring the reaction to completion by, if necessary, reducing the pressure.
The subsequent quaternization is also carried out by known processes. According to the invention, this involves adding equimolar amounts of the quaternizing agent, with stirring and optionally under pressure, to the ester, optionally with use of a solvent, preferably isopropanol, ethanol, 1,2-propylene glycol and/or dipropylene glycol, at 60-90xc2x0 C., and monitoring completion of the reaction by checking the overall amine value.
Examples of quaternizing agents which can be used in combination with the compounds of general formula (I) and/or (II), are organic or inorganic acids, but preferably short-chain dialkyl phosphates and sulfates, such as, in particular, dimethyl sulfate (DMS), diethyl sulfate (DES), dimethyl phosphate, diethyl phosphate, short-chain halogenated hydrocarbons, in particular methyl chloride or dimethyl sulfate.
For individual applications, the surfactants, viscosity regulators, preservatives, corrosion inhibitors, dyes, perfumes, plant extracts or other additives customary in the respective fields can be used. These agents are sufficiently known to the person skilled in the art from current practice and the corresponding specialist literature and require no further explanation.
For the preparation of the quaternary ammonium compounds, methylethanol-isopropanolamine (MEIPA) and fatty acids were reacted and quaternized by the processes generally known to those of skill in the art and discussed above. Preferred fatty acids are as follows (in the following tables xe2x80x2 indicates mono-unsaturation, xe2x80x3 indicates di-unsaturation). In all of these cases, the compounds were quaternized with dimethylsulfate so that, referring to formulas (I) and (II), R is xe2x80x94CH3 and Axe2x88x92 is CH3SO4xe2x88x92).
A. Tallow fatty acids with an acid number of 202-208, an iodine value of 36-44, and a carbon chain distribution as follows.
B. Palm fatty acids with an acid number of 205-212, an iodine value of 30-40, and a carbon chain distribution as follows.
C. Palm fatty acids with an acid number of 205-215, an iodine value of 15-25 and a carbon chain distribution as follows.
D. Rapeseed oil fatty acid (RFA) with an acid value of 190-210 and an iodine value of 85-110 and a carbon chain distribution as follows.
In the following description, Components A-G are produced by reacting MEIPA with fatty acid mixtures FA-I, FA-II, FA-III, or FA-IV as indicated in the table, in the molar ratio of MEIPA to acid mixtures indicated.
Component A: [MEIPA :FA I=1:1.6]+Axe2x88x92
Component B: [MEIPA :FA I=1:2]+Axe2x88x92
Component C: [MEIPA :FA II=1:1.6]+Axe2x88x92
Component D: [MEIPA :FA II=1:2]+Axe2x88x92
Component E: [MEIPA: FA III=1: 1.6]+Axe2x88x92
Component P: [MEIPA: FA III=1: 2]+Axe2x88x92
Component G: [MEIPA: FA IV=1: 2]+Axe2x88x92
The fabric softener is prepared by emulsification or dispersion of the respective individual components in water. In this connection, it is possible to use the methods which are customary in this field. The process usually involves initially introducing water which has been preheated to about 10xc2x0 C. below the clear melting point of the softener, dispersing one after the other, with thorough stirring, firstly the dye solution, then the antifoam emulsion, which is optionally required, and finally the clear melt of the individual softener. After some of an electrolyte solution has been added, perfume oil is metered in, followed by the remaining electrolyte solution, and the mixture is then left to cool to room temperature with stirring. The fabric softeners according to the invention may comprise said components within the limits customary in this field, such as, for example, 15-22% by weight of the compounds of the general formulas (I) and/or (II); 2-5% by weight of a solvent such as, in particular, isopropanol, ethanol, propylene glycol and dipropylene glycol; 0.1-1.5% by weight of an alkali metal salt and/or alkaline earth metal salt; 0.5-1.5% by weight of perfume oil and topped up to 100% by weight (to 100) with water.
As is known in the state of this art for suitable fabric softening formulations, the fabric softeners according to the present invention are according to proper procedure added during the last rinse stage of the washing cycle. The concentration to use depends on the dilution with water, but appropriate levels should lie in the range of 0.1 to 10 grams of fabric softener per liter of wash water.
Determination of the Rewetting Power
In accordance with DIN 53924, the test fabric (about 3 kg of cotton twill fabric, 100% cotton; supplier: WFK-Testgewebe GmbH, Krefeld) is washed twice using 100 g of test detergent (WFK, April 1988 formula) in each case and then twice without detergent (in each case 95xc2x0 C. program with prewash). The test fabric is hung up to dry at room temperature for one day. When dry, test strips measuring about 25 cm in length and 1.5 cm in width are cut out. It must be ensured that all test strips of one test series have the threads running the same way.
The test strips are marked with a ball-point pen. Holes are punched at both ends of the test strips; a border about 5 millimeters in width should be left at the edge of the fabric.
The beakers are initially charged with the corresponding amount of demineralized water, and 0.025%, based on the solids content, of the product to be tested is stirred in. A control experiment is carried out by initially introducing demineralized water into the dipping bath.
In each case, 10 test strips are introduced into these liquors, stirred for 5 minutes at about 50 rpm using a magnetic stirrer and then left for 5 minutes without stirring. The test strips are then hung up to dry at room temperature for 24 hours. After this time, a line parallel to the long outer edges is drawn on the smooth side of each of the strips using a water-soluble felt-tip pen.
The test strips treated in this way (control+test product(s)) are now attached to the immersion device. It must be ensured that the strips do not become elongated. The immersion device with the strips is placed into the tank filled with demineralized water (corresponds to about 10 liters) to a height of 8 centimeters and left there for 5 minutes. 10 minutes after the immersion device has been removed from the tank, the level reached by the water, which can be seen from the migrating felt-tip pen dye, is determined in millimeters. It must be ensured that the lower holed edge on the upper side contacts directly with the hanging hooks in order to avoid reading errors. The demineralized water must be replaced after each experiment.
Evaluation
According to the invention, this method may result in slight scattering, which must be taken into consideration in the calculation by indicating the standard deviation.       Rewetting    ⁢          xe2x80x83        ⁢    power    ⁢          xe2x80x83        ⁢          (      %      )        =            Height      ⁢              xe2x80x83            ⁢      reached      ⁢                        xe2x80x83                ⁢                  xe2x80x83                    ⁢      by      ⁢                        xe2x80x83                ⁢                  xe2x80x83                    ⁢      A      ⁢              xe2x80x83            ⁢              (        mm        )            xc3x97      100      ⁢      %              Height      ⁢              xe2x80x83            ⁢      reached      ⁢              xe2x80x83            ⁢      by      ⁢              xe2x80x83            ⁢      BW      ⁢              xe2x80x83            ⁢              (        mm        )            
where BW is the arithmetic mean of the height reached by the water (dye) in millimeters for the controls; and A is the arithmetic mean of the height reached by the water (dye) in millimeters for the samples of a fabric softener.
Fabric-feel Test Procedure
3 kg of the test fabric (xe2x80x9cDuosoftxe2x80x9d fabric, 100% cotton; supplier: Vossen) are washed with 2xc3x97100 grams of test detergent (WFK, April 1988 formula) and then twice without detergent (in each case 95xc2x0 C. program with prewash, time approximately 2 h); spinning speed: 1200 rpm.
A fixed predetermined liquor volume of 151 (Miele W 719) results in a liquor ratio of 5:1. After washing, the test fabric is hung up to dry at room temperature for one day and then stored at room temperature until treated.
To immerse the fabric, the calculated amounts of the fabric softener are introduced into the beakers at 15-20xc2x0 C. and made up to 2 liters with tap water which has a German hardness of about 9xc2x0 and is at 15-20xc2x0 C. The mixture is then stirred on a magnetic stirrer until homogeneous dispersions or solutions form.
A control experiment is carried out by introducing only tap water in the dipping bath. One section of test fabric is immersed per rinsing bath. After 10 minutes, the fabric is taken out of the rinsing bath, lightly wrung out, lightly shaken three times and hung up to dry as a single layer for 48 hours at room temperature.
The test fabric treated in this way is cut into 10 equal sections (about 16 centimetersxc3x9725 centimeters). Each test subject is given a new test section for assessment. It is important to prevent the test sections from becoming xe2x80x9csoft through handlingxe2x80x9d after several handle tests.
The test fabrics treated with different fabric softeners are now compared in pairs. The evaluation consists in the test subjects assigning whole points between 0 and 5; 0 points indicating poor (hard) and 5 points indicating good (soft).
Evaluation
The differences between the individual pairs are in each case placed in the second column (difference points). The difference is then assigned to the better product. The more difference points a product has, the better its handle.
In a preferred embodiment of the invention, the composition includes water in the formulation. In another preferred embodiment of the invention, the composition comprises a mixture of two or more different compounds of formulas (I) and/or (II).
In an embodiment of the present invention, the composition further comprises water. In an embodiment of the present invention, the second surfactant comprises a conventional quaternary compound. In another embodiment of the present invention, the composition does not contain a significant amount of silicones. In yet another embodiment of the present invention, the composition comprises a mixture of two or more different compounds of formulas (I) and/or (II). In a further embodiment of the present invention, the composition comprises a mixture of two or more different conventional quaternary compounds.
It can be seen from the above, that ranges in amounts given for each ingredient or component of a composition or formulation set forth herein in certain circumstances may be theoretically capable of adding up to a sum of greater than 100%. As would be appreciated by those of skill in the art, it is understood that such impossible formulations (that is, those formulations whose component amounts add to a sum greater than 100%) are excluded from the claims and disclosure. For example, a formulation having components A and B, where the amount of A is said to range from 25% to 75% and the amount of B is said to range from 25% to 55%, if containing 65% of A, is understood to have 35% or less of B in that formulation, so that the sum of A and B does not exceed 100%. Thus, all formulations or compositions presented herein whose component amounts add to a sum less than or equal to 100% are understood as being part of the claims and disclosure.
The present disclosure shows that the compounds and formulations of the present invention may be used for many purposes and suitable additives may be incorporated therein based on the ultimate application. Such ingredients, for example, may contribute significantly to the ease of formulation, stability, dispersibility, fluidity, and the performance properties of the compositions.
In one aspect, the present invention provides compounds and formulations that have the ability to impart to fabric (that is, articles of clothing, textiles, and so forth), properties including softness to the touch, ease of handling, increased lubricity, and a reduced tendency to carry or pick up static electricity. One form in the compounds and formulations of the present invention are provided is as a liquid, for instance, as an emulsion or as a solution/suspension of the desired components. During use, an appropriate controlled amount of the liquid formulation is employed, for example, by pouring the formulation directly into the washing machine. Typically, the formulation is dispensed during the rinse cycle of the washing machine, either poured in by hand or metered in by an appropriate automatic metering device with which the washing machine is equipped.
In addition, the present invention also provides compounds and formulations that may find use as textile treatments to add lubricity and finishing to the fabric prior to shipping the textile to market, particularly when used in conjunction with a resin bath. In such an application, the textile mill would typically apply the formulation in dilute emulsions and rapidly dry the excess water from the fabric to lubricate the fibers and give it a surface finish.
The present invention also provides compounds and formulations that are useful in personal care products such as hair or skin conditioners. In this application, the present invention provides formulations that impart softness, lubricity, and improve the surface appearance of the skin or hair. The hair conditioners additionally reduce the tendency for tangling, improve the manageability, and impart a soft feel to the hair strands. Such hair conditioners are applied as dilute emulsions to the hair following its wash or may be incorporated into a combined conditioner and shampoo composition, also known as a conditioning shampoo, two-in-one shampoo, or two-in-one. Such hair and skin conditioning formulations typically incorporate effective amounts, for example, 0.1 wt. % to 10 wt. % or more, of emollients, humectants, and/or slip and conditioning agents, such as organopolysiloxanes and the like, to create formulations that are monophasic and can be made to be translucent or even clear. Compounds suitable for use as emollients, humectants and conditioners in formulations for skin care or hair care can be found in the CTFA Cosmetic Ingredient Dictionary, 3d Edition, and in the CTFA Cosmetic Ingredient Handbook, which are hereby incorporated by reference in their entireties.
The compositions of the present invention are particularly useful in applications that take advantage of their ability to disperse hydrophobic material, to stabilize foam, and to enhance the penetration and wetting exhibited by the compositions. Examples of such compositions and applications are set forth below, each revealing an additional aspect of the present invention.
The compounds and formulations of the present invention may be used as oil dispersants and oil slick dispersant formulations for application onto oil, for example, onto a film of oil, to disperse the oil.
The compounds and formulations of the present invention may also be used as oil well stimulation and oil recovery aids for injection into oil wells in order to penetrate into the surface of the borehole and assist liberation of crude oil from the matrix material into the borehole, from which it can be brought to the surface.
In addition, the compounds and formulations of the present invention may be used as vehicles for hydrophobic sheeting agents such as mineral oil and silicone oil. Such oils can readily be dispersed in compositions, according to the present invention, and the resulting formulations are highly satisfactory when sprayed or otherwise applied to a surface, such as a freshly washed automobile surface, to impart a lustrous, water-repellent film to the surface.
The compounds and formulations of the present invention may also be used as rinse aids, such as used in automatic dishwashers, wherein application of the composition of the present invention disperses residual hydrophobic matter, including cleaner residues and films.
Furthermore, the compounds and formulations of the present invention may be used as paper deinking and ink flotation agents for treating waste inked paper by addition to the pulp slurry such that the ink is liberated from the paper and prevented from redepositing onto the paper. In this application, the ink is typically dispersed or even fully solubilized in the resulting solution when the ink particles are floated from the fibers.
The compounds and formulations of the present invention may also be used as asphalt emulsion agents for emulsifying finely divided asphalt (at loadings of typically 1-20 wt. %), with or without particulate filler such as sand, in an aqueous phase which comprises the composition according to the present invention.
Moreover, the compounds and formulations of the present invention may be used as corrosion inhibitor agents for application to any surface to which one desires to apply a film that protects against corrosion. The composition would typically contain an effective amount of a hydrophobic corrosion inhibiting material, such as liquid or waxy-solid fatty ester, paraffinic hydrocarbon, silicone, or the like, dispersed in a composition according to the present invention.
In addition, the compounds and formulations of the present invention may be used with ore flotation agents for separating ore from rock. Such floatation agents might include, for example, the agent available from Witco Corporation under the tradename WITCAMINE(copyright) AL42-12. Typically, the ore floatation agent (a collector or frother, depending on the characteristics of the particular separation desired in the flotation cell) or mixture thereof, which is a relatively hydrophobic material, is dispersed in a composition according to the invention and an effective amount is added (on a batch or continuous basis) to the ore separation cell. This permits the formulator to improve the dispersibility of the hydrophobic ore floatation agent, which often improves the performance of the mineral separation by improving the efficiency of the floatation agent""s dispersibility. This can enable the operator to use smaller amounts of the ore floatation agent to achieve the desired purpose because there is a higher concentration of active ingredients available.
In addition, the compounds and formulations of the present invention may be used as suspension concentrates and emulsifiable concentrates of herbicides, pesticides, miticides, fungicides, or bactericides, wherein one or more liquid or solid, generally hydrophobic, active ingredients are dispersed in a composition according to the present invention. The resulting concentrate can be applied as a concentrate on or around desired vegetation, but is more often mixed with water (for example, at the point of use) to form a final dilute formulation having the desired concentration of active ingredient(s). This application takes advantage of the noteworthy property of this invention that addition of the water does not disrupt the monophasic state, nor the fluidity, of the formulation.
As noted above, the compositions and formulations of the present invention can also optionally contain other components, depending on the additional properties one may wish to provide in the finished composition. Such additional components include, but are not limited to, additional coupling agents and solvents, additional quaternary ammonium compounds, additional surfactants, hydrocarbon actives, perfumes, preservatives including bacteriocides and fungicides, insect and moth repelling agents, polymeric soil release agents, antistatic agents, dyes and colorants, especially bluing agents, viscosity control agents, antioxidants, silicones, defoaming agents, antifoaming agents, emulsifiers, brighteners, opacifiers, freeze-thaw control agents, shrinkage control agents, aloe, humectants, skin protectants, feel modifiers, and mixtures thereof.
Each of the foregoing reactions can be carried out in solvent or in solvent-free conditions, in each case employing conditions well established for the respective reactions in this field.
The products as described herein exhibit a number of desirable properties making them particularly suitable for formulation into commercial products such as fabric softeners and other commercial products, as mentioned above.
Most notably, the compounds of formulas (I) and (II) can readily be formulated into useful compositions such as aqueous compositions, which achieve the desired functionality and which are clear, that is, transparent or translucent. This property can be realized at a variety of concentrations of active ingredient, with or even without special solvents or coupling agents. In addition, microemulsion formulations can be made that improve the ease of application and effectiveness of the resulting formulation.
Emulsion or microemulsion formulations according to the present invention have many applications, for example, as car xe2x80x9ccheaterxe2x80x9d wax spray technology to improve beading and act as a drying aid, as fabric softeners, and as personal care products, for example, as a moisturizer/conditioner if the compound of formulas (I) and/or (II) is not skin irritating. In addition, such emulsions or microemulsions may find uses as emulsifiers for silicone oils and pesticides, and as emulsifiers/softeners for textile finishing. Generally such formulations include three components: (a) compound of formulas (I) and/or (II), (b) a solvatrope or coupling agent and blends thereof, and (c) an oil or hydrophobic organic component and blends thereof, which are blended in water. These microemulsion formulations give stable, clear (translucent) products that do not go through thick or viscous gel phases but disperse readily and quickly into very fine particle size microemulsions when diluted or dispersed in water. These microemulsions have many additional advantages over conventional microemulsions, such as the products sold by Witco Corporation under the tradename CARSPRAY(trademark): reduced particle size, improved beading and sheeting over, and improved biodegradability, especially when used with methyl ester oils.
If the resulting formulation is intended to be used as a personal care formulation, the amount of the compound of formulas (I) and/or (II) is about 0.1 wt. % to about 65 wt. % of the formulation, preferably about 0.1 wt. % to about 25 wt. %, and most preferably about 0.1 wt. % to about 5 wt. %; the amount of solvatrope or coupling agent is about 0.1 wt. % to about 65 wt. % of the formulation, preferably about 0.1 wt. % about 25 wt. %, and most preferably about 0.1 wt. % to about 0.5 wt. %; the amount of oil or hydrophobic organic component is about 0.1 wt. % to 65 wt. % of the formulation, preferably about 0.1 wt. % to about 25 wt. %, and most preferably about 0.1 wt. % to about 5 wt. %; and the amount of water is about 20 to 99.7 wt. % of the formulation, preferably about 35 wt. % to about 99.7 wt. %, and most preferably about 65 wt. % to about 99.7 wt. %.
If the resulting formulation is intended to be used in a car drying aid formulation or other application, the amount of the compound of formulas (I) and/or (II) is about 5 wt. % to about 50 wt. % of the formulation, preferably about 10 wt. % to about 30 wt. %, and most preferably about 15 wt. % to about 25 wt. %; the amount of solvatrope or coupling agent is about 2 wt. % to about 15 wt. % of the formulation, preferably about 3 wt. % about 10 wt. %, and most preferably about 6 wt. % to about 10 wt. %; the amount of oil or hydrophobic organic component is about 5 wt. % to 50 wt. % of the formulation, preferably about 10 wt. % to about 30 wt. %, and most preferably about 15 wt. % to about 20 wt. %; and the amount of water is about 10 to 70 wt. % of the formulation, preferably about 20 wt. % to about 60 wt. %, and most preferably about 30 wt. % to about 50 wt. %.
Although the compounds of formulas (I) and/or (II) have many potential uses, in particular, they exhibit highly satisfactory fabric softening capabilities. Thus, the compounds of formulas (I) and/or (II), as well as mixtures of such compounds, can be advantageously formulated appropriately into products useable as fabric softeners. Preferred emulsions useful as fabric softener compositions can contain about 2 wt. % to about 80 wt. %, preferably 5 wt. % to 30 wt. %, and more preferably 6 wt. % to 25 wt. %, of one or more compounds corresponding to formulas (I) and/or (II). In general, higher solids contents can be provided more easily with lower degrees of quaternization. On the other hand, higher degrees of quaternization (such as a degree of quaternization approaching 2.0 for a diamine), lead to aqueous formulations wherein the maximum acceptable solids content without excessive solubility problems is lower.
The compounds of formulas (I) and/or (II) can be formulated into compositions, including clear fabric softener compositions. Such fabric softening composition would typically include water and one or more of the solvents which are conventionally used in formulating fabric softeners. Examples of such solvents include ethanol, isopropanol, hexylene glycol, propylene glycol, diethylene glycol, or similar solvent of mixture thereof, as a concentrate or more dilute form, depending on the application. Selection of a suitable solvent for a particular application is well-known to those of skill in the art. Such formulations generally comprise about 10 wt. % up to about 50 wt. % of one compound of formulas (I) and/or (II) or a mixture thereof.
The compounds of formulas (I) and/or (II) can be formulated with greater ease than is encountered with conventional quaternary ammonium fabric softener actives. Most conventional quaternary ammonium compounds exhibit a tendency to form a gel during dilution with water when formulated in clear formulations. When formulated in clear formulations, however, the compounds of formulas (I) and/or (II) show very little gelation, or no gelation at all, during dilution with water, even cold water, which would be expected to provoke gelation. This freedom from a tendency to gel means that compositions including compounds of formulas (I) and/or (II) can be prepared at active concentrations of 40 wt. % or higher, for example, even 50 wt. % or higher. The preparation itself of such formulations is much simpler: the freedom from gelation means that when a formulator chooses to manufacture a more concentrated product for resale to the consumer, there is no need for special treatment to deal with gel formation. Also, the freedom from gel formation means that the consumer can use the more concentrated product directly without concern that a gelled byproduct would form. For example, the consumer could add a concentrated fabric softener composition according to the present invention directly into the wash water in the wash or rinse cycle, without any apprehension that a gel will form that that would reduce softening efficiency or leave a deposit on the clothes.
It should be noted that the ability of the compounds of formulas (I) and/or (II) to form a clear formulation, at lower and at higher concentrations, extends also to formulations which also contain one or more other quaternary ammonium compounds as fabric softener co-actives, as well as other additives as disclosed herein.
Additional conventional quaternary ammonium compounds or salts may be present with the compound or compounds of formulas (I) and/or (II) in accordance with the present invention. The compounds presented below are only examples of conventional quaternary compounds that are suitable for use in the formulations of the present invention. As with the compounds of formulas (I) and/or (II), these conventional quaternary ammonium compounds (quats or salts) may have an anion to provide electrical neutrality and, in general, such anion may be any anion which is not deleterious to the properties of the overall compound. Thus, in the structural formulas (i) to (xxiii) below, the counteranion, whether designated as Axe2x88x92 or not shown but understood, may be selected, without limitation, from the group consisting of fluoride, chloride, bromide, iodide, chlorite, chlorate, hydroxide, hypophosphite, phosphite, phosphate, carbonate, formate, acetate, lactate, and other carboxylates, oxalate, methyl sulfate, ethyl sulfate, benzoate, and salicylate, and the like. Preferred examples of the anions are chloride, bromide, methyl sulfate, ethyl sulfate, and salicylate. If the anion is monovalent (has a charge of xe2x88x921), Axe2x88x92 represents the anion group, if the anion is divalent (has a charge of xe2x88x922), Axe2x88x92 represents half of the anion group, if the anion is trivalent (has a charge of xe2x88x923), Axe2x88x92 represents a third of the anion group, and so on.
The conventional quats that may be formulated with the compounds of formulas (I) and/or (II) in accordance with the present invention include, but are not limited to, nitrogenous compounds selected from the group consisting of quaternized or acid salt derivatives of:
(i) alkylenediamines, including compounds of the formula: 
wherein each R1 is an acyclic alkyl or alkylene C12-C21 hydrocarbon group, each Z is xe2x80x94(R2O)0xe2x88x924H, or xe2x80x94R2H, and R2 and R3 are divalent C1-C6 alkylene groups;
(ii) substituted imidazoline compounds having the formula: 
(iii) reaction products of higher fatty acids with alkylenetriamines in, for example, a molecular ratio of about 2:1, the reaction products containing compounds of the formula: 
wherein R1, R2 and R3 are defined as above; and
(iv) substituted imidazoline compounds having the formula: 
wherein G is xe2x80x94Oxe2x80x94 or xe2x80x94NHxe2x80x94 and R1 and R2 are defined as above; and mixtures thereof.
Preferred examples of compounds of structural formula (i) are those derived from hydrogenated tallow fatty acids and the hydroxyalkylalkylenediamine is N-2-hydroxyethylethylenediamine, such that R1 is an aliphatic C15-C21 hydrocarbon group, and R2 and R3 are divalent ethylene groups.
A preferred example of a compound of structural formula (iii) is stearic hydroxyethyl imidazoline, wherein R1 is an aliphatic C21 hydrocarbon group and R2 is a divalent ethylene group.
A preferred example of compounds of structural formula (iii) is N,Nxe2x80x3-ditallowalkanoyldiethylenetriamine where R1 is an aliphatic C15-C21 hydrocarbon group and R2 and R3 are divalent ethylene groups.
A preferred example of compounds of structural formula (iv) is 1-tallowamidoethyl-2-tallowimidazoline wherein R1 is an aliphatic C15-C21 hydrocarbon group and R2 is a divalent ethylene group.
Both N,Nxe2x80x3-ditallowalkanoyldiethylenetriamine and 1-tallowethylamido-2-tallowimidazoline are reaction products of tallow fatty acids and diethylenetriamine, and are precursors of the cationic fabric softening agent methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate (see xe2x80x9cCationic Surface Active Agents as Fabric Softeners,xe2x80x9d R. R. Egan, Journal of the American Oil and Chemicals Society, January 1978, pages 118-121). N,Nxe2x80x3-ditallowalkanoyldiethylenetriamine and 1-tallowamidoethyl-2-tallowimidazoline can be obtained from Witco Corporation. Methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate is available from Witco Corporation under the tradename VARISOFT(copyright) 475.
Other suitable quats are those containing one long chain acyclic aliphatic C8-C22 hydrocarbon group, selected from the group consisting of:
(v) acyclic quaternary ammonium salts having the formula: 
wherein R4 is an acyclic aliphatic C8-C22 hydrocarbon group, alkyl, benzyl or (C4-C18 alkyl)xe2x80x94(OCH2CH2)2xe2x88x923xe2x80x94, R5 and R6 are C1-C4 saturated alkyl or hydroxyalkyl groups, and Axe2x88x92 is an anion as defined above;
(vi) substituted imidazolinium salts having the formula: 
wherein R1 is an acyclic alkyl or alkylene C12-C21 hydrocarbon group, R7 is hydrogen or a C1-C4 saturated alkyl or hydroxyalkyl group, and Axe2x88x92 is an anion as defined above;
(vii) substituted imidazolinium salts having the formula: 
wherein R1, R2, R5, and Axe2x88x92 are as defined above;
(viii) alkylpyridinium salts having the formula: 
wherein R4 is an acyclic aliphatic C8-C22 hydrocarbon group and Axe2x88x92 is an anion as defined above; and
(ix) alkanamide alkylene pyridinium salts having the formula: 
wherein R1 is an acyclic aliphatic C12-C21 hydrocarbon group, R2 is a divalent C1-C6 alkylene group, and Axe2x88x92 is an anion as defined above; and mixtures thereof.
Examples of compounds of structural formula (v) are the monoalkyltrimethylammonium salts including monotallowtrimethylammonium chloride, mono(hydrogenated tallow)-trimethylammonium chloride, palmityltrimethylammonium chloride and soyatrimethylammonium chloride, available from Witco Corporation under the tradenames ADOGEN(copyright) 471, ADOGEN(copyright) 441, ADOGEN(copyright) 444, and ADOGEN(copyright) 415, respectively. In these compounds, R4 is an acyclic aliphatic C16-C18 hydrocarbon group, and R5 and R6 are methyl groups. In this application, mono(hydrogenated tallow)trimethylammonium chloride and monotallowtrimethylammonium chloride are preferred. Other examples of compounds of structural formula (v) are behenyltrimethylammonium chloride wherein R4 is a C22 hydrocarbon group, which is available from the Humko Chemical Division of Witco Corporation under the tradename KEMAMINE(copyright) Q2803-C; soyadimethylethylammonium ethylsulfate wherein R4 is a C16-C18 hydrocarbon group, R5 is a methyl group, R6 is an ethyl group, and Axe2x88x92 is an ethylsulfate anion; and methyl bis(2-hydroxyethyl)octadecylammonium chloride wherein R4 is a C18 hydrocarbon group, R5 is a 2-hydroxyethyl group and R6 is a methyl group.
An example of a compound of structural formula (vii) is 1-ethyl-1-(2-hydroxyethyl)-2-isoheptadecylimidazolinium ethylsulfate wherein R1 is a C17 hydrocarbon group, R2 is an ethylene group, R5 is an ethyl group, and Axe2x88x92 is an ethylsulfate anion.
Other quats useful in the present invention include cationic nitrogenous salts having two or more long chain acyclic aliphatic C8-C22 hydrocarbon groups or one long chain acyclic aliphatic C8-C22 hydrocarbon group and an arylalkyl group. Examples include:
(x) acyclic quaternary ammonium salts having the formula: 
wherein each R4 is an acyclic aliphatic C8-C22 hydrocarbon group, R5 is a C1-C4 saturated alkyl or hydroxyalkyl group, R8 is selected from the group consisting of R4 and R5 groups, and Axe2x88x92 is an anion as defined above;
(xi) diamido quaternary ammonium salts having the formula: 
wherein each R1 is an acyclic alkyl or alkylene C12-C21 hydrocarbon group, each R2 is a divalent alkylene group having 1 to 3 carbon atoms, R5 and R9 are C1-C4 saturated alkyl or hydroxyalkyl groups, and Axe2x88x92 is an anion as defined above;
(xii) alkoxylated diamido quaternary ammonium salts having the formula: 
wherein n is equal to 1 to about 5, and R1, R2, R5, and Axe2x88x92 are as defined above;
(xiii) quaternary ammonium compounds having the formula: 
wherein R4 is an acyclic aliphatic C8-C22 hydrocarbon carbon group, each R5 is a C1-C4 saturated alkyl or hydroxyalkyl group, and Axe2x88x92 is an anion as defined above;
(xiv) amide-substituted imidazolinium salts having the formula: 
wherein each R1 is an acyclic aliphatic C12-C21 hydrocarbon group, R2 is a divalent alkylene group having 1 to 3 carbon atoms, and R5 and Axe2x88x92 are as defined above, or R5 is xe2x80x94H; and
(xv) ester-substituted imidazolinium salts having the formula: 
wherein R1, R2, R5, and Axe2x88x92 are as defined above; and mixtures thereof.
Examples of compounds of structural formula (x) are the well-known dialkyldimethylammonium salts including ditallowdimethylammonium chloride, ditallowdimethylammonium methylsulfate, distearyldimethylammonium chloride, di(hydrogenated tallow)dimethylammonium chloride, dibehenyldimethylammonium chloride. Di(hydrogenated tallow)dimethylammonium chloride and ditallowdimethylammonium chloride are preferred. Examples of commercially available dialkyldimethylammonium salts usable in the present invention are di(hydrogenated tallow)dimethylammonium chloride (available from Witco Corporation under the tradename ADOGEN(copyright) 442); ditallowdimethylammonium chloride (available from Witco Corporation under the tradename ADOGEN(copyright) 470); distearyldimethylammonium chloride (available from Witco Corporation under the tradename AROSURF(copyright) TA-100); dicocodimethyl ammonium chloride (available from Witco Corporation under the tradename ADOGEN(copyright) 462), and dibehenyldimethylammonium chloride, wherein R4 is an acyclic aliphatic C22 hydrocarbon group (available from the Humko Chemical Division of Witco Corporation under the tradename KEMAMINE(copyright) Q-2802C).
Examples of compounds of structural formula (xi) are methylbis(tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate and methylbis(hydrogenated tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate, wherein R1 is an acyclic aliphatic C15-C17 hydrocarbon group, R2 is an ethylene group, R5 is a methyl group, R9 is a hydroxyalkyl group and Axe2x88x92 is a methylsulfate anion; both of these materials are available from Witco Corporation under the tradenames VARISOFT(copyright) 222 and VARISOFT(copyright) 110, respectively.
An example of a compound of structural formula (xiii) is dimethylstearylbenzylammonium chloride, wherein R4 is an acyclic aliphatic C18 hydrocarbon group, R5 is a methyl group and Axe2x88x92 is chloride, which is available from Witco Corporation under the tradename VARISOFT(copyright) SDC.
Examples of compounds of structural formula (xiv) are 1-methyl-l-tallowamidoethyl-2-tallowimidazolinium methylsulfate and 1 -methyl-1-(hydrogenated tallowamidoethyl)-2-(hydrogenated tallow)imidazolinium methylsulfate wherein R1 is an acyclic aliphatic C15-C17 hydrocarbon group, R2 is an ethylene group, R5 is a methyl group and Axe2x88x92 is a chloride anion; available from Witco Corporation under the tradenames VARISOFT(copyright) 475 and VARISOFT(copyright) 445, respectively.
Additional examples of quaternary ammonium compounds useful in the present invention include:
(xvi) compounds having the formula: 
wherein R1, is selected from the group consisting of: (a) xe2x80x94CH3, xe2x80x94CH2CH3, xe2x80x94CH2CH2OH, or straight chain aliphatic hydrocarbon groups each of which contains from 12 through 24 carbon atoms, (b) ether groups each of which has the structure: R13O(CH2O)yxe2x80x94, (c) amide groups each of which has the structure: 
and (d) ester groups each of which has the structure: 
R12 is a straight chain aliphatic hydrocarbon group containing from 8 to 32 carbon atoms,
R13 is a straight chain aliphatic hydrocarbon group containing from 8 to 21 carbon atoms,
R14 is a straight chain aliphatic hydrocarbon group containing from 7 to 17 carbon atoms,
Z is an alkoxy group containing one oxygen atom and either two or three carbon atoms,
Axe2x88x92 is an anion as defined above,
m is an integer from 1 through 12, and
y is an integer which is either 2 or 3.
Yet additional examples of fabric softening compounds useful in the present invention include:
(xvii) compounds having the formula: 
wherein R15 is hydrogen or C1-C4 alkyl, 
each R16 is C1-C4 allyl or
each R17 is a C8-C28 alkyl or alkenyl group,
R18 is hydrogen or C1-C4 alkyl,
each y is 0 or 1, x is 0 or 1, and each n is from 1 to 6;
(xviii) amides represented by the structural formula: 
wherein R19 and R20 are selected independently from the group consisting of C1-22 alk(en)yl aryl or alkyl aryl groups, R21 is hydrogen or a C1-22 alk(en)yl, aryl or alkyl-aryl group or is Oxe2x80x94R22, wherein R22 is a C1-22 alk(en)yl, aryl or alkyl-aryl group, and R21 and R22 optionally contain 1 to 10 alkylene oxide units or functional groups selected from hydroxy, amine, amide, ester, and ether groups; the aryl groups being possibly derived from heterocyclic compounds; at least one of the R19 and R20 groups contains 10 or more carbon atoms; and where the sum of carbon atoms in R19+R20+R21 is equal to or greater than 14. Preferably, the sum of carbon atoms in R19+R20 is equal to or greater than 16. Examples of compounds of structural formula (xviii) include N,N-ditallow acetamide, N,N-dicoconut acetamide, N,N-dioctadecyl propanamide, N-dodecyl-N-octadecyl acetamide, N-hexadecyl-N-dodecyl butanamide, N,N-ditallow benzamide, N,N-dicoconut benzamide, and N,N-ditallow 2-phenyl acetamide.
Additional fabric softening compounds useful in the present invention include all ester quaternaries, including but not limited to:
(xix) compounds of the following structural formulas: 
wherein
each R21 is independently a saturated or unsaturated alkyl or alkylene radical containing 12 to 22 carbon atoms;
each Q21 is independently an alkl group containing 1 to 4 carbon atoms, benzyl, xe2x80x94CH2CH2OH, xe2x80x94CH2CH(OH)CH3, or R21xe2x80x94C(O)xe2x80x94(Oxe2x80x94(Alk21))1-4xe2x80x94;
each Alk21 is independently C2H4, C3H6 or C4H8; and
Axe2x88x92 is an anion as defined above;
(xx) compounds of the formula: 
wherein each A22 is the same or different and each is alkyl containing up to 3 carbon atoms, benzyl, or Hxe2x80x94(Alk22xe2x80x94O)1-3xe2x80x94Alk22xe2x80x94wherein each Alk22 signifies xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH(CH3)CH2xe2x80x94, or xe2x80x94CH2CH(CH3)xe2x80x94, provided further that one of the A22 can be hydrogen;
D is methyl, ethyl, propyl, xe2x80x94(CH2)1-3COOxe2x80x94, benzyl or hydrogen;
i is 0 or 1 and j is 0 or 1, provided that the sum of (i+j) is 1 or 2;
each X22 is a straight or branched saturated or unsaturated aliphatic group containing up to 3 carbon-carbon double bonds and containing 11 to 23 carbon atoms;
n is two minus the number of xe2x80x94(CH2)1-3COOxe2x80x94 substituents present; and
Axe2x88x92 is an anion as defined above;
(xxi) compounds of the formula:
R23xe2x80x94[C(O)O(CH2)1-5]0-1xe2x80x94C(O)NH(CH2)2-5xe2x80x94N(R23a)(R23b) xe2x80x94(CH2)2-5xe2x80x94OC(O)R23Axe2x88x92
wherein
each R23 is independently straight or branched alkyl or alkenyl containing 8 to 22 carbon atoms;
R23a is straight or branched alkyl or hydroxyalkyl containing 1 to 3 carbon atoms, benzyl, or xe2x80x94C2H4OC(O)R26, wherein R26 is straight or branched alkyl or alkenyl containing 8 to 22 carbon atoms;
R23b is xe2x80x94H, xe2x80x94CH3, xe2x80x94C2H5 or benzyl; and
Axe2x88x92 is an anion as defined above; and
(xxii) compounds of the following structural formulas: 
wherein
each R24 is independently straight or branched alkyl or alkenyl containing 1 to 8 carbon atoms and 0 to 3 hydroxyl groups;
each R25 is straight or branched alkyl or alkenyl containing 10 to 22 carbon atoms and 0 to 3 hydroxyl groups;
each Y is xe2x80x94Oxe2x80x94C(O)xe2x80x94 or xe2x80x94C(O)xe2x80x94Oxe2x80x94;
each m is 1 to 3;
each n is from 1 to 8; and
Axe2x88x92 is an anion as defined above.
Preferred examples of compounds of structural formulas (xxii) include methyl diethanolamine (MDEA) ester quats, triethanolamine (TEA) ester quats, for example, di-(tallow carboxyethyl) hydroxyethyl methylammonium methosulfate, available from Witco Corporation under the tradename REWOQUAT(trademark) WE 16, or epichlorohydrin-based ester quats, all of which are used and accepted as fabric softeners worldwide because of their favorable biodegradation profiles, but usually lack the optimum softening performance of other quats.
Additional fabric softening compounds useful in the present invention include polyester polyquaternary compounds, including but not limited to:
(xxiii) compounds of the following structural formula: 
wherein each of R* and R** is independently a linear, branched or cyclic alkylene group containing 2 to 12 carbon atoms, wherein no two nitrogen atoms are separated by fewer than 2 carbon atoms;
each of A1, A2, A3, A4, and A4 is independently a straight or branched alkylene containing 2 to 4 carbon atoms;
each of R1, R2, R3, R4, and R5 is independently xe2x80x94H or RAC(O)xe2x80x94 wherein RA is straight or branched alkyl or alkenyl containing 7 to 21 carbon atoms and 0 to 4 carbon-carbon double bonds; provided that at least one of R1, R2, R3, R4, or R5 is RAC(O)xe2x80x94;
each of Q1, Q2 and Q3 is independently xe2x80x94H, xe2x80x94CH3, xe2x80x94C2H5, xe2x80x94C3H7, xe2x80x94C4H5, benzyl, CH2COOH, or xe2x80x94CH2COOAxe2x88x92; or, if R* is a xe2x80x94CH2CH2xe2x80x94 group, Q1 and Q3 together or Q1 and Q2 together may be a xe2x80x94CH2CH2xe2x80x94 group to form a six-membered piperazine ring; or, if R** is a xe2x80x94CH2CH2xe2x80x94 group, Q3 and Q3 together may be a xe2x80x94CH2CH2xe2x80x94 group to form a six-membered piperazine ring;
m is 0to4;
r is 0 to 2;
each of v, w, x, y, and z is independently 1 to 8;
i is 0 to 1, j is 0 to 1, and each k is 0 to 1, and the sum of (i+j+k) is 0 to 4;
each Axe2x88x92 is independently an anion as defined below; and
n is the number of moles of Axe2x88x92 needed to give the compound of structural formula
(xiii) a zero net charge. Compounds of structural formula (xxiii), formulations thereof, and uses thereof, form the subject matter of pending U.S. application Ser. No. 09/170,623, filed on Oct. 13, 1998.
In a preferred embodiment of this invention, fabric softener formulations and other formulations which may be clear (translucent or transparent) and easily dispersed in water can be provided by including an appropriate amount of one or more straight or branched alkyl diols containing 4 to 12 carbon atoms, and/or alkoxylates of such diols with up to 40 alkoxy units per diol moiety, wherein the alkoxylate chains are composed of alkoxy units which are ethoxy, propoxy or butoxy or mixtures thereof, and preferably ethoxy or propoxy. These diol and diol alkoxylate hydrotropes or coupling agents are added to the formulations to increase the amount of the relatively water-insoluble surfactants that can be solubilized into the system. In most cases, they do not act as surfactants to lower surface tension but they often allow surfactants in the presence of salts or electrolytes to be added and subsequently dispersed into water at higher concentrations or at lower viscosities of the formulation than is otherwise achieved using only surfactant and water. These coupling agents assist surfactants by increasing the surfactant""s solubility in water and its stability in the formulation, especially in the presence of salts, electrolytes and/or pH agents.
These diols and alkoxylates correspond to structural formula (T)
HOxe2x80x94(Xxe2x80x94O)xxe2x80x94RTxe2x80x94(Oxe2x80x94Y)yxe2x80x94OHxe2x80x83xe2x80x83(T)
wherein each X and each Y is ethylene (that is, xe2x80x94C2H4xe2x80x94), propylene (that is, xe2x80x94C3H6xe2x80x94), or butylene (that is, xe2x80x94C4H8xe2x80x94); x is 0-40; y is 0-40; the sum (x+y) is 0-40; and RT is straight, branched or cyclic alkyl containing 4 to 12 carbon atoms. Preferably, RT contains 7-12 or even 7-9 carbon atoms.
The alkylene residue RT in structural formula (T) represents a saturated, straight-chain, branched-chain, or cyclic moiety containing 4 to 12 carbon atoms. It is preferred that RT is branched, wherein the term xe2x80x9cbranchedxe2x80x9d is intended to encompass structures having one side alkyl chain, more than one side alkyl chain, or one or more side alkyl chains, one or more of which is itself branched. Branched structures include cyclic structures substituted with one or more alkyl groups, the alkyl groups being straight or branched. Examples of suitable RT groups include such groups as xe2x80x94CH2CH(CH3)CH2xe2x80x94, xe2x80x94(CH2)6xe2x80x94, xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94C(CH3)2CH2xe2x80x94, xe2x80x94CH2CH(CH2CH3)CH2CH2CH2CH2xe2x80x94, xe2x80x94CH2C(CH3)2xe2x80x94CH2xe2x80x94CH2C(CH3)2CH(CH(CH3)2)xe2x80x94, xe2x80x94CH2CH(CH2CH2CH2CH3)xe2x80x94, and xe2x80x94CH(CH2)2CH(CH2)2xe2x80x94.
In the alkoxylated diols, the number of repeating units in each poly(alkoxy) chain can be up to 40 but it is preferred that each chain contains 1 to 10 repeating alkoxy units or more preferably 1 to 5 alkoxy units. The preferred alkoxy chains are poly(ethoxy), or are composed of 1 to 2 ethoxy units capped with a chain of 1 to 5 propoxy units.
Compounds of structural formula (T) defined above are in many instances commercially available. Compounds of structural formula (T) can be prepared in straightforward manner familiar to those of ordinary skill in this art by obtaining or preparing the corresponding precursor diol of structural formula HOxe2x80x94RTxe2x80x94OH, and then alkoxylating the precursor diol with a stoichiometrically appropriate number of moles of the desired corresponding alkylene oxide, such as ethylene oxide, propylene oxide, and/or butylene oxide. In those cases where it is desired to alkoxylate only one of the hydroxyl groups on the precursor diol, in some embodiments the alkoxylation will preferentially occur at only one of the hydroxyl groups, particularly where one of them is a primary hydroxyl and the other is a secondary hydroxyl. However, in those cases where both hydroxyl groups on the precursor diol might tend to alkoxylate but alkoxylation at only one of the hydroxyl groups is desired, the hydroxyl group at which alkoxylation is desired not to occur can be protected by preliminarily reacting it with a suitable protecting group such as a lower alkyl moiety or an esterifying substituent. Thereafter, following the alkoxylation, the protecting group is removed in a known manner.
Preferred examples of compounds of the foregoing structural formula (T) include any one, or mixtures, of 2,2,4-trimethyl-1,3-pentanediol (TMPD) and/or 2-ethylhexane-1,3-diol, and/or the reaction product of TMPD and/or 2-ethylhexane-1,3-diol with 1 to 10 moles of ethylene oxide, and preferably with 1 to 5 moles of ethylene oxide, as well as analogs alkoxylated with other C3 or C4 alkyl oxides or mixtures of any of C2, C3 and/or C4 alkyl oxides. Since the diol which is alkoxylated includes one primary hydroxyl group and one secondary hydroxyl group, the alkoxylation proceeds predominantly at the primary hydroxyl group.
The compositions which contain one or more compounds of formulas (I) and/or (II) can also contain one or a mixture of compounds of structural formula (E)
RE1xe2x80x94C(O)Oxe2x80x94RE2xe2x80x94(OC(O)RE3)0-1xe2x80x83xe2x80x83(E)
wherein RE1 is straight, cyclic or branched alkyl containing 1-15 carbon atoms, and RE1 is substituted with 0 to 3 hydroxyl groups; and wherein RE2 is straight, cyclic or branched alkyl containing 1 to 10 carbon atoms, and RE2 is substituted with 0 to 3 hydroxyl groups, and RE2 can optionally be substituted with a group of the structure xe2x80x94OC(O)xe2x80x94RE3 wherein RE3 is straight, cyclic or branched alkyl containing 1 to 15 carbon atoms and is optionally substituted with a hydroxyl group.
Preferred compounds of structural formula (E) include those wherein RE2 contains 2 or 3 carbon atoms, for example, glycol and glyceryl derivative, or RE2 contains about 8 carbon atoms, for example, derivatives of 2,2,4-trimethylpentanediol or of 2-ethylhexanediol. Preferred compounds of structural formula (E) include 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, hydroxypivalyl hydroxypivalate, and the monoester of TMPD with hydroxypivalic acid.
Formulations can also contain what may be termed aesthetic additives to provide properties such as fragrance, preservative, viscosity control, and color. Such additives are discussed below. The formulations according to the present invention generally exhibit highly satisfactory viscosities, generally as pourable and even sprayable fluids.
Other suitable non-quaternary compound surfactants, whether anionic, cationic, zwitterionic, nonionic, or amphoteric, may be used in combination with the compounds and formulations of the invention, depending on the application.
1. General Surfactants
For example, in a fabric softening application, suitable anionic surfactants may include, without limitation, the alkylbenzene sulfonates, xcex1-olefin sulfonates, and xylene sulfonates available from Witco Corporation under the WITCONATE(copyright) trademark. While these surfactants may be unsuitable for personal care applications because they may cause skin and eye irritation, surfactants suitable for personal care applications may be used in other non-personal care applications.
2. Personal Care Suractants
For personal care applications, suitable anionic surfactants would include, without limitation, ammonium lauryl sulfate, sodium lauryl sulfate, any xcex1-olefin sulfonate, ammonium laureth sulfate (2 or 3 moles), sodium laureth sulfate (2 or 3 moles), sodium myristyl sulfate, sodium myristeth sulfate (1-4 moles), ammonium xylene sulfonate, sodium xylene sulfonate, TEA dodecylbenzene sulfonate, TEA lauryl sulfate, ammonium pareth sulfate, sodium pareth sulfate, sodium oleth sulfate, derivatives of any of the forgoing, and similar compounds known to those of skill in the art, and mixtures thereof. For personal care applications, suitable amphoteric surfactants or non-ionic surfactants include betaines, sulfosuccinates, mono- and diglycerides, glycinates, sugars and derivatives thereof, hydroxysultaines, mono- and diacetates, ethoxylated derivatives of any of the forgoing, and similar compounds known to those of skill in the art, and mixtures thereof. Preferred surfactants include cocamidopropyl betaine, lauramidopropyl betaine, ricinoleamidopropyl betaine, myristamidopropyl betaine, paimamidopropyl betaine, stearamidopropyl betaine, behenamidopropyl betaine, erucamidopropyl betaine, cocamidopropyl hydroxysultaine, myristamidopropyl hydroxysultaine, palmamidopropyl hydroxysultaine, stearamidopropyl hydroxysultaine, behenamidopropyl hydroxysultaine, erucamidopropyl hydroxysultaine, disodium lauroamphodiacetate, disodium cocamphodiacetate, disodium myristamphodiacetate, disodium palmamphodiacetate, disodium stearamphodiacetate, disodium behenamphodiacetate, disodium erucamphodiacetate, sodium lauryl amphoacetate, sodium cocamphoacetate, sodium cocoamphopropionate, sodium laurylamphopropionate, disodium lauroamphodipropionate, sodium lauryl sulfosuccinate, disodium laureth sulfosuccinate, cocobetaine, laurylbetaine, myristylbetaine, stearylbetaine, behenylbetaine, PEG 1-300 glyceryl cocoate, PEG 1-300 glyceryl tallowate, PEG 1-500 hydrogenated glyceryl palmitate, coco-glucoside, lauryl glucoside, decyl glucoside, and mixtures thereof.
Other surfactants that may be added to these systems include, but are not limited to, alkanolamides such as almondamide diethanolamine (DEA), behenamide DEA, cocamide DEA, hydrogenated tallowamide DEA, isostearamide DEA, lactamide DEA, lauramide DEA, linoleamide DEA, myristamide DEA, oleamide DEA, palmamide DEA, palmitamide DEA, ricinoleamide DEA, soyamide DEA, stearamide DEA, tallamide DEA, and tallowamide DEA. Preferred alkanolamides include acetamide monoethanolamine (MEA), behenamide MEA, cocamide MEA, hydroxystearamide MEA, isostearamide MEA, lactamide MEA, lauramide MEA, linoleamide MEA, myristamide MEA, oleamide MEA, palmamide MEA, palmitamide MEA, ricinoleamide MEA, stearamide MEA, tallowamide MEA, undecylenamide MEA, cocamide monoisopropylamine (MIPA), hydroxyethyl stearamide MIPA, isostearamide MIPA, lauramide MIPA, linoleamide MIPA, myristamide MIPA, oleamide MIPA, palmamide MIPA, ricinoleamide MIPA, and stearamide MIPA. Some of these alkanolamides are available from Witco Corporation under the WITCAMIDE(copyright) tradename.
In addition, various amine oxides may be used in these systems. Preferred amine oxides include, but are not limited to, behenamine oxide, cocamidopropylamine oxide, cocamine oxide, decylamine oxide, dihydroxyethylcocamine oxide, dihydroxyethyllauramine oxide, dihydroxyethyltallowamine oxide, hydrogenated palm kernel amine oxide, hydrogenated tallowamine oxide, isostearamidopropylamine oxide, lauramidopropylamine oxide, lauramine oxide, myristamidopropylamine oxide, myristamine oxide, oleamidopropylamine oxide, oleamine oxide, palmitamidopropylamine oxide, palmitamine oxide, soyamidopropylamine oxide, stearamidopropylamine oxide, stearamine oxide, tallowamidopropylamine oxide, tallowamine oxide, and undecylenamidopropylamine oxide. Several of these materials are available from Witco Corporation under the VAROX(copyright) tradename.
Emollients and emulsifiers are also typically used in personal care formulations in combination with the polyester amine compounds and polyquaternary compounds of the invention, depending on the application.
1. Personal Care Emollients
The preferred embodiment of this invention may also be used in emulsions that can be used as skin or hair conditioners which can take the form of lotions, creams, leave-on products, and rinse-off products. These systems may also include additional products that may improve the feel and conditioning, or the emolliency of skin and hair. In addition to some of the materials mentioned above that can also function as conditioning agents, preferred additives for this use include, but are not restricted to, acetylated lanolin, aminopropyl dimethicone, ammonium hydrolyzed collagen, ammonium lauroyl sarcosinate, amodimethicone, amodimethicone/dimethicone copolyol, amodimethicone hydroxystearate, capryloyl hydrolyzed collagen, cetyl alcohol, cetyl esters, cetyl laurate, cocamidopropyl dimethylamine dihydroxymethylpropionate, cocoyl hydrolyzed soy protein, collagen, disodium cocoamphodiacetate, disodium cocoamphodipropionate, dioctyl dimerate, ditridecyl adipate, glycerine, glyceryl oleate, glyceryl stearate, hydrogenated soybean oil, hydrogenated tallow glycerides, isocetyl stearate, jojoba (Buxus chinensis) oil, keratin, lanolin, milk protein, mineral oil, oat (Avena sativa) protein, octyl cocoate, oleyl myristate, oleyl stearate, palm alcohol, palm glycerides, panthenol, PEG-10, PEG-32, PEG-100, PEG-200, petrolatum, PPG-6-sorbeth-245, stearyl citrate, tridecyl stearate, urea, vegetable oil, and wheat amino acids. Some of these products are available from Witco Corporation under the KEMSTRENE(copyright), WITCONOL(trademark), STARFOL(copyright), and KEMESTER(copyright) tradenames.
2. Personal Care Emulsifiers
Such emulsions usually include emulsifiers to form and preserve the emulsion. In addition to some of the materials previously mentioned that also act as emulsifiers, some preferred emulsifiers for this use include, but are not restricted to beheneth-5, beheneth-10, beheneth-20, butylglucoside caprate, ceteareth-2, ceteareth-10, ceteareth-18, ceteth-10, ceteth-16, corn oil PEG-8 esters, C9-11 pareth-3, C11-15 pareth-5, C11-15 pareth-12, C12-13 pareth-2, C12-13 pareth-10, C12-13 pareth-15, deceth-4, deceth-6-di-C12-13 pareth-6 phosphate, di-C12-15 pareth-8 phosphate, glyceryl cocoate, glyceryl laurate, glyceryl oleate, isoceteth-10, isodeceth-6, isosteareth-10, laureth4, laureth-5, laureth-10, octyldodeceth-10, octyldodeceth-20, oleoyl ethyl glucoside, oleth-2, oleth4, PEG-8 caprate, PEG-8 castor oil, PEG-7 cocamide, PEG-11 cocamide, PEG-15 cocoate, PEG-20 dilaurate, PEG-32 dilaurate, PEG-8 dioleate, PEG-2 distearate, PEG-8 distearate, PEG-8 glyceryl laurate, PEG-15 glyceryl laurate, PEG4 isostearate, PEG4 laurate, PEG-5 octanoate, PEG-9 oleamide, PEG-5 oleate, PEG-20 palmitate, PEG-6 stearate, PEG-16 tallate, polysorbate 20, polysorbate 80, steareth-10, trideceth-5, and undeceth-9.
Other additives and adjuvants can be optionally added to the compounds and formulations of the present invention for their known purposes. Such additives and adjuvants include but are not limited to, perfumes, preservatives including bacteriocides and fungicides, insect and moth repelling agents, polymeric soil release agents, antistatic agents, dyes and colorants, especially bluing agents, viscosity control agents, antioxidants, silicones, defoaming agents, antifoaming agents, emulsifiers, brighteners, opacifiers, freeze-thaw control agents, shrinkage control agents, aloe, humectants, skin protectants, feel modifiers, waxes, glycerine, vitamins and extracts, and mixtures thereof. The identity and amounts of the additives and adjuvants used would depend on the application of the formulation and its desired properties. The additives and adjuvants are well-known to those of skill in the art and the additives and adjuvants listed below are not meant to be an exhaustive list but merely a guide to the types of additives that would typically be used.
1. Perfumes
As noted above, perfumes or fragrance materials may be added to the compositions and formulations of the present invention. The selection of the perfume or perfumes is based upon the application, the desired effect on the consumer, and preferences of the formulator. The perfume selected for use in the compositions and formulations of the present invention contains ingredients with odor characteristics which are preferred in order to provide a fresh impression on the surface to which the composition is directed, for example, those which provide a fresh impression for fabrics if a fabric softener treatment formulation is prepared. Such perfume is preferably present at a level of from about 0.01% to about 5% , preferably from about 0.05% to about 3% , more preferably from about 0.1% to about 2%, by weight of the total composition.
Preferably, the perfume is composed of fragrance materials selected from the group consisting of aromatic and aliphatic esters having molecular weights from about 130 to about 250; aliphatic and aromatic alcohols having molecular weights from about 90 to about 240; aliphatic ketones having molecular weights from about 150 to about 260; aromatic ketones having molecular weights from about 150 to about 270; aromatic and aliphatic lactones having molecular weights from about 130 to about 290; aliphatic aldehydes having molecular weights from about 140 to about 200; aromatic aldehydes having molecular weights from about 90 to about 230; aliphatic and aromatic ethers having molecular weights from about 150 to about 270; and condensation products of aldehydes and amines having molecular weights from about 180 to about 320; and mixtures thereof. The selection of such perfumes and fragrance materials are well-known to those of skill in the art, both for desired scent and appropriate scent impact. For example, when high initial perfume odor impact on fabrics is desired, it is preferable to select a perfume containing perfume ingredients which are not too hydrophobic. The degree of hydrophobicity of a perfume ingredient can be correlated with its octanol/water partitioning coefficient P, the ratio between its equilibrium concentration in octanol and in water. Thus, a perfume ingredient with a greater partitioning coefficient P is more hydrophobic and a perfume ingredient with a smaller partitioning coefficient P is more hydrophilic; a selection based on the application and intended effect may be made accordingly. For example, in a fabric application, the preferred perfume ingredients would have an octanol/water partitioning coefficient P of about 1,000 or smaller.
2. Preservatives
Optionally, solubilized, water-soluble preservatives can be added to the present invention. Preservatives are especially preferred when organic compounds that are subject to microorganisms are added to the compositions of the present invention, especially when they are used in aqueous compositions. When such compounds are present, long term and even short term storage stability of the compositions and formulations becomes an important issue since contamination by certain microorganisms with subsequent microbial growth often results in an unsightly and/or malodorous solution. Therefore, because microbial growth in these compositions and formulations is highly objectionable when it occurs, it is preferable to include a solubilized water-soluble, antimicrobial preservative, which is effective for inhibiting and/or regulating microbial growth in order to increase storage stability of the preferably clear and often aqueous compositions and formulations of the present invention.
Typical microorganisms that can be found personal care products include bacteria, for example, Bacillus thuringiensis (cereus group) and Bacillus sphaericus, and fungi, for example, Aspergillus ustus. Bacillus sphaericus is one of the most numerous members of Bacillus species in soils. In addition, microorganisms such as Escherichia coli and Pseudomonas aerupinosa are found in some water sources, and can be introduced during the preparation of aqueous solutions of the present invention.
It is preferable to use a broad spectrum preservative, for example, one that is effective on both bacteria (both gram positive and gram negative) and fungi. A limited spectrum preservative, for example, one that is only effective on a single group of microorganisms, for example, fungi, can be used in combination with a broad spectrum preservative or other limited spectrum preservatives with complimentary and/or supplementary activity. A mixture of broad spectrum preservatives can also be used.
Antimicrobial preservatives useful in the present invention can be biocidal compounds, that is, substances that kill microorganisms, or biostatic compounds, that is, substances that inhibit and/or regulate the growth of microorganisms. Preferred antimicrobial preservatives are those that are water-soluble and are effective at low levels. In general, the water-soluble preservatives that may be used include organic sulfur compounds, halogenated compounds, cyclic organic nitrogen compounds, low molecular weight aldehydes, quaternary compounds, dehydroacetic acid, phenyl and phenoxy compounds, and mixtures thereof. Examples of preservatives useful in the present invention include, but are not limited to, the short chain alkyl esters of p-hydroxybenzoic acid (commonly known as parabens); N-(4-chlorophenyl)-N-(3,4-dichlorophenyl) urea (also known as 3,4,4xe2x80x2-trichlorocarbanilide or triclocarban); 2,4,4xe2x80x2-trichloro-2xe2x80x2-hydroxydiphenyl ether, commonly known as triclosan); a mixture of about 77% 5-chloro-2-methyl4-isothiazolin-3-one and about 23% 2-methyl-4-isothiazolin-3-one, a broad spectrum preservative available from the Rohm and Haas Company as a 1.5% aqueous solution under the tradename KATHON(copyright) CG; 5-bromo-5-nitro-1,3-dioxane, available from Henkel Corporation under the tradename BRONIDOX(copyright) L; 2-bromo-2-nitropropane-1,3-diol, available from Inolex Chemical Company under the tradename BRONOPOL(trademark); 1,1xe2x80x2-hexamethylenebis(5-(p-chlorophenyl)biguanide) (commonly known as chlorhexidine) and its salts, for example, with acetic and digluconic acids; a 95:5 mixture of 1,3-bis(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidinedione and 3-butyl-2-iodopropynyl carbamate, available from Lonza Inc. under the tradename GLYDANT(copyright) Plus; N-[1,3-bis(hydroxymethyl)2,5-dioxo 4imidazolidinyl]-N,Nxe2x80x2-bis(hydroxy-methyl) urea, commonly known as diazolidinyl urea, available from Sutton Laboratories, Inc. under the tradename GERMALL(copyright) II; N,Nxe2x80x3-methylenebis[Nxe2x80x2-[1-(hydroxymethyl)-2,5-dioxo-4-imidazolidinyl]urea] (commonly known as imidazolidinyl urea), available, for example, from 3V-Sigma under the tradename ABIOL(trademark), from Induchem under the tradename UNICIDE(copyright) U-13, and from Sutton Laboratories, Inc. under the tradename GERMALL(copyright) 115; polymethoxy bicyclic oxazolidine, available from Hxc3xcls America Inc. under the tradename NUOSEPT(copyright); formaldehyde; glutaraldehyde; polyaminopropyl biguanide, available from ICI Americas, Inc. under the tradename COSMOCIL(copyright) CQ or from Brooks Industries Inc. under the tradename MIKROKILL(trademark); dehydroacetic acid; and mixtures thereof. In general, however, the preservative can be any organic preservative material which is appropriate for the application, for example, in a fabric softening application such preservative will preferably not cause damage to fabric appearance, for example, discoloration, coloration, or bleaching of the fabric.
If the antimicrobial preservative is included in the compositions and formulations of the present invention, it is preferably present in an effective amount, wherein an xe2x80x9ceffective amountxe2x80x9d means a level sufficient to prevent spoilage or prevent growth of inadvertently added microorganisms for a specific period of time. Preferred levels of preservative are from about 0.0001% to about 0.5%, more preferably from about 0.0002% to about 0.2%, most preferably from about 0.0003% to about 0.1%, by weight of the composition.
Bacteriostatic effects can sometimes be obtained for aqueous compositions by adjusting the composition pH to an acid pH, for example, less than about pH 4, preferably less than about pH 3. Low pH for microbial control is not a preferred approach in the present invention because the low pH can cause chemical degradation of the cyclodextrins. Therefore, aqueous compositions of the present invention should have a pH greater than about 3.0, preferably greater than about 4.0, more preferably greater than about 4.5. As stated above, it is preferable to use the preservative at an effective amount, as defined hereinabove. Optionally, however, the preservative can be used at a level which provides an antimicrobial effect on the treated fabrics.
3. Antistatic Agents
The composition of the present invention can optionally contain an effective amount of antistatic agent to provide the treated clothes with in-wear static. Preferred antistatic agents are those that are water soluble in at least effective amount, such that the composition remains a clear solution. Examples of these antistatic agents include monoalkyl cationic quaternary ammonium compounds, for example, mono(C10-C14 alkyl)trimethyl ammonium halide, such as monolauryl trimethyl ammonium chloride, hydroxycetyl hydroxyethyl dimethyl ammonium chloride (available from Henkel Corporation under the tradename DEHYQUART(copyright) E), and ethyl bis(polyethoxyethanol) alkylammonium ethylsulfate (available from Witco Corporation under the tradename VARIQUAT(copyright) 66), polyethylene glycols, polymeric quaternary ammonium salts (such as those available from Rhxc3x4ne-Poulenc Corporation under the MIRAPOL(copyright) tradename), quaternized polyethyleneimines, vinylpyrrolidone/methacrylamidopropyltrimethylamrnonium chloride copolymer (available from GAF Corporation under the tradename GAFQUAT(copyright) HS-100), triethonium hydrolyzed collagen ethosulfate (available from Maybrook Inc. under the tradename QUAT-PRO(trademark) E), and mixtures thereof.
It is preferred that a no foaming, or low foaming, agent is used, to avoid foam formation during fabric treatment. It is also preferred that polyethoxylated agents such as polyethylene glycol or VARIQUAT(copyright) 66 are not used when xcex1-cyclodextrin is used. When an antistatic agent is used it is typically present at a level of from about 0.05% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.3% to about 3%, by weight of the composition.
4. Dyes and Colorants
Colorants and dyes, especially bluing agents, can be optionally added to the compositions of the present invention for visual appeal and performance impression. When colorants are used, they are used at extremely low levels to avoid fabric staining. Preferred colorants for use in the present compositions are highly water-soluble dyes, for example, LIQUITINT(copyright) dyes available from Milliken Chemical Company. Non-limiting examples of suitable dyes are, LIQUITINT(copyright) Blue HP, LIQUITINT(copyright) Blue 65, LIQUITINT(copyright) Patent Blue, LIQUITINT(copyright) Royal Blue, LIQUITINT(copyright)D Experimental Yellow 8949-43, LIQUITINT(copyright) Green HMC, LIQUITINT(copyright) Yellow II, and mixtures thereof. Any dye can be used in the compositions of the present invention, but nonionic dyes are preferred to decrease interaction with dye transfer inhibitor. Useful acid dyes include: Polar Brilliant Blue, and DandC Yellow #10, both supplied by Hilton Davis Chemical Company. Nonionic LIQUITINT(copyright) dyes supplied by Milliken Chemical Company are also useful.
For many personal care products using the present invention, colorants are also added at extremely low levels. Color additives for products to be marketed in the United States are named in compliance with Title 21 of the U.S. Code of Federal Regulations. Suitable colors include, but are not limited to, Acid Black 1, Acid Blue 3, Acid Blue 9 Aluminum Lake, Acid Blue 74, Acid Green 1, Acid Orange 6, Acid Red 14 Aluminum Lake, Acid Red 27, Acid Red 27 Aluminum Lake, Acid Red 51, Acid Violet 9, Acid Yellow 3, Acid Yellow 3 Aluminum Lake, Acid Yellow 73, Aluminum Powder, Basic Blue 6, Basic Yellow 11, xcex2-Carotene, Brilliant Black 1, Bromocresol Green, Chromium Oxide Greens, CI 12010, CI 12120, CI 28440, CI 71105, Curry Red, DandC Blue No. 1 Aluminum Lake, DandC Blue No. 4, DandC Brown No. 1, DandC Green No. 3 Aluminum Lake, DandC Green No. 5, DandC Orange No. 4 Aluminum Lake, DandC Red No. 6, DandC Red No. 6 Aluminum Lake, DandC Violet No. 2, DandC Yellow No. 7, DandC Yellow No. 11, DandC Blue No. 1, FDandC Yellow No. 5 Aluminum Lake, iron oxides, Pigment Orange-5, Pigment Red 83, Pigment Yellow 73, Solvent Orange 1, Solvent Yellow 18, ultramarines, and zinc stearate.
5. Insect and Moth Repelling Agents
The composition of the present invention can optionally contain an effective amount of insect or moth repelling agents. Typical insect and moth repelling agents are pheromones, such as anti-aggregation pheromones, and other natural and/or synthetic ingredients. Preferred insect and moth repellent agents useful in the composition of the present invention are perfume ingredients, such as citronellol, citranellal, citral, linalool, cedar extract, geranium oil, sandalwood oil, 2-(diethylphenoxy)ethanol, 1-dodecene, and the like. Other examples of insect and/or moth repellents useful in the composition of the present invention are disclosed in U.S. Pat. Nos. 4,449,987; 4,693,890; 4,696,676; 4,933,371; 5,030,660; and 5,196,200; and in B. D. Mookherjee et al., xe2x80x9cSemio Activity of Flavor and Fragrance Molecules on Various Insect Speciesxe2x80x9d, published in Bioactive Volatile Compounds from Plants, ASC Symposium Series 525, R. Teranishi, R. G. Buttery, and H. Sugisawa (eds.), 1993, pp. 35-48. All of these patents and publications are herein incorporated by reference in their entireties. When an insect and/or moth repellent is used it is typically present at a level of from about 0.005 wt. % to about 3 wt. % of the composition.
6. Polymeric Soil Release Agents
Soil release agents, usually polymers, are especially desirable additives at levels of from about 0.05 wt. % to about 5 wt. %, preferably from about 0.1 wt. % to about 4 wt. %, more preferably from about 0.2 wt. % to about 3 wt. %. Suitable soil release agents are disclosed in U.S. Pat. Nos. 4,702,857; 4,711,730; 4,713,194; 4,877,896; 4,956,447; and 4,749,596, all of these patents being herein incorporated by reference in their entireties.
Especially desirable optional ingredients are polymeric soil release agents comprising block copolymers of polyalkylene terephthalate and polyoxyethylene terephthalate, and block copolymers of polyalkylene terephthalate and polyethylene glycol. The polyalkylene terephthalate blocks preferably comprise ethylene and/or propylene groups. Many such soil release polymers are nonionic, for example, the nonionic soil release polymer is described in U.S. Pat. No. 4,849,257, which patent is herein incorporated by reference in its entirety.
The polymeric soil release agents useful in the present invention can include anionic and cationic polymeric soil release agents. Suitable anionic polymeric or oligomeric soil release agents are disclosed in U.S. Pat. No. 4,018,569, which patent is herein incorporated by reference in its entirety. Other suitable polymers are disclosed in U.S. Pat. No. 4,808,086, which patent is herein incorporated by reference in its entirety. Suitable cationic soil release polymers are described in U.S. Pat. No. 4,956,447, which patent has already been herein incorporated by reference.
7. Viscosity Control Agents
Viscosity control agents can be organic or inorganic in nature and may either lower or raise the viscosity of the formulation. Examples of organic viscosity modifiers (lowering) are aryl carboxylates and sulfonates (for example, benzoate, 2-hydroxybenzoate, 2-aminobenzoate, benzenesulfonate, 2-hydroxybenzenesulfonate, 2-aminobenzenesulfonate, etc.), fatty acids and esters, fatty alcohols, and water-miscible solvents such as short chain alcohols. Examples of inorganic viscosity control agents are water-soluble ionizable salts. A wide variety of ionizable salts can be used. Examples of suitable salts are the halides and acetates of ammonium ion and the group IA and IIA metals of the Periodic Table of the Elements, for example, calcium chloride, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, ammonium chloride, sodium bromide, potassium bromide, calcium bromide, magnesium bromide, ammonium bromide, sodium iodide, potassium iodide, calcium iodide, magnesium iodide, ammonium iodide, sodium acetate, potassium acetate, or mixtures thereof. Calcium chloride is preferred. The ionizable salts are particularly useful during the process of mixing the ingredients to make the compositions herein, and later to obtain the desired viscosity. The amount of ionizable salts used depends on the amount of active ingredients used in the compositions and can be adjusted according to the desire of the formulator. Typical levels of salts used to control the composition viscosity are from 0 to about 10 wt. %, preferably from about 0.01 wt. % to about 6 wt. %, and most preferably from about 0.02 wt. % to about 3 wt. % of the composition.
Viscosity modifiers (raising) or thickening agents can be added to increase the ability of the compositions to stably suspend water-insoluble articles, for example, perfume microcapsules. Such materials include hydroxypropyl substituted guar gum (such as that available from Rhxc3x4ne-Poulenc Corporation under the tradename JAGUAR(copyright) HP200), polyethylene glycol (such as that available from Union Carbide Corporation under the tradename CARBOWAX(copyright) 20M), hydrophobic modified hydroxyethylcellulose (such as that available from the Aqualon Company under the tradename NATROSOL(copyright) Plus) and/or organophilic clays (for example, hectorite and/or bentonite clays such as those available from the Rheox Company under the tradename BENTONETI(trademark) 27, 34 and 38 or from Southern Clay Products under the tradename BENTOLITE(trademark) L; and those described in U.S. Pat. No. 4,103,047, which is herein incorporated by reference in its entirety). These viscosity raisers (thickeners) are typically used at levels from about 0.5 wt. % to about 30 wt. %, preferably from about 1 wt. % to about 5 wt. %, more preferably from about 1.5 wt. % to about 3.5 wt. %, and most preferably from about 2 wt. % to about 3 wt. %, of the composition.
8. Pearlizing and Opacifying Agents
Examples of pearlizing or opacifying agents that can be added to the compositions of this invention include, but are not restricted to, glycol distearate, propylene glycol distearate, and glycol stearate. Some of these products are available from Witco Corporation under the KEMESTER(copyright) tradename.
9. Vitamins and Extracts
In personal care applications, vitamins and extracts are often used in the formulations thereof. Examples of vitamins that can be added to the compositions of this invention include, but are not restricted to, vitamins A1, A2, B1, B2, B6, B12, C, D, E, H, and K, the provitamins, salts, derivatives, and complexes thereof, and mixtures thereof. Examples of extracts that can be added to the compositions of this invention include, but are not restricted to, rosemary extract, carrot extract, Camelina saliva, camomile extract, egg yolk extract, elm extract, acacia extract, rose extract, lilac extract, licorice extract, lemon extract, orange extract, lime extract, linden extract, melon extract, peach extract, orchid extract, orris extract, and the like, and mixtures thereof.
10. Antioxidants
Examples of antioxidants that can be added to the compositions of this invention are propyl gallate, available from Eastman Chemical Products, Inc. under the tradenames TENOX(copyright) PG and TENOX(copyright) S-1, and dibutylated hydroxytoluene, available from UOP Inc. under the tradename SUSTANE(copyright) BHT.
11. Silicones
The present compositions can contain silicones to provide additional benefits, for example, in a fabric application they may provide ease of ironing and improved fabric absorbency. As used herein, the term xe2x80x9csiliconesxe2x80x9d comprises cationic and amphoteric silicones, polysiloxanes, and polysiloxanes having hydrogen-bonding functional groups consisting of amino, carboxyl, hydroxyl, ether, polyether, aldehyde, ketone, amide, ester, and thiol groups. Such polysiloxanes include, but are not limited to, polyether-modified polysiloxanes, aminu-modified polysiloxanes, epoxy-modified polysiloxanes, polyhydrido-modified polysiloxanes, phenol-derivative-modified polysiloxanes, ABA-type polysiloxanes, [AB]N-type polysiloxanes, amino [AB]N-type polysiloxanes, including those available from OSi Specialties, Inc. (a division of Witco Corporation), under the SILWET(copyright), NUWET(copyright), NUDRY(trademark), NUSOFT(trademark), MAGNASOFT(copyright) tradenames.
Suitable silicones may include polydimethylsiloxanes of viscosity of from about 100 centistokes (cs) to about 100,000 cs, preferably from about 200 cs to about 60,000 cs and/or silicone gums. These silicones can be used in emulsified form, which can be conveniently obtained directly from the suppliers. Examples of these preemulsified silicones are the 60% emulsion of polydimethylsiloxane (350 cs) sold by Dow Corning Corporation under the tradename DOW CORNING(copyright) 1157 Fluid and the 50% emulsion of polydimethylsiloxane (10,000 cs) sold by General Electric Company under the tradename GENERAL ELECTRIC(copyright) SM 2140 silicones. The optional silicone component can be used in an amount of from about 0.1 wt. % to about 6 wt. % of the composition.
Silicone foam suppressants can also be used. These are usually not emulsified and typically have viscosities of from about 100 cs to about 10,000 cs, preferably from about 200 cs to about 5,000 cs. Very low levels are used, typically from about 0.01% to about 1%, preferably from about 0.02% to about 0.5%. Another preferred foam suppressant is a silicone/silicate mixture, for example, Dow Corning""s ANTIFOAM(trademark) A.
The pH (10% solution) of the compositions of this invention is generally adjusted to be in the range of from about 2 to about 7, preferably from about 2.4 to about 6.5, more preferably from about 2.6 to about 4. Adjustment of pH is normally carried out by including a small quantity of free acid in the formulation. Because no strong pH buffers are present, only small amounts of acid are required. Any acidic material can be used; its selection can be made by anyone skilled in the softener arts on the basis of cost, availability, safety, etc. Among the acids that can be used are methyl sulfonic, hydrochloric, sulfuric, phosphoric, citric, maleic, and succinic. For the purposes of this invention, pH is measured by a glass electrode in a 10% solution in water of the softening composition in comparison with a standard calomel reference electrode.
12. Lubrication and Slip Additives
Compositions and formulations of the present invention can contain additives such as water, insoluble organics such as fatty acids, fatty esters, triglycerides, oils, alcohols, fatty alcohols, fatty amines and derivatives, amides, hydrocarbons, mineral oils, waxes, and the like, and mixtures thereof, as lubrication and slip agents.
13. Dye Transfer Inhibitors
Compositions and formulations of the present invention can contain ethoxylated amines, amphoterics, betaines, polymers such as polyvinylpyrrolidone, and other ingredients that inhibit dye transfer.